(High Temperature Materials Division Outstanding Achievement Award) Semiconducting Properties and Defect Disorder of Titanium Dioxide

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This work reports defect disorder of TiO2 in terms of defect diagrams showing the effect of oxygen activity and temperature on the concentration of both ionic and electronic defects and the related semiconducting properties. It is also shown that imposition of the gas/solid equilibrium for the TiO2-O2 system should be considered in terms of the equilibration kinetics of both fast and slow defects. In the latter case the time required to reach the equilibrium at 1323 K is up to 4000 h. The effect of indium on surface vs. bulk electrical properties is considered in terms of both thermoelectric power and electrical conductivity determined at 1023 K – 1273 K in the gas phase of controlled oxygen activity [10-16 Pa<p(O2)<105 Pa]. It is shown that the effect of oxygen activity on the electrical properties is consistent with a dual mechanism of indium incorporation, involving acceptor energy levels in the bulk and donor levels at the interface. This results in the formation of a quasi-isolated thin interface layer that differs from the bulk in the semiconducting properties and the related defect disorder. This conclusion is supported by surface analysis of In-doped TiO2 using secondary ion mass spectrometry (SIMS) showing strong indium surface segregation. It is shown that the semiconducting properties may be modified in a controlled manner by defect engineering. It is also shown that segregation may be used as the technology in processing TiO2 with desired surface vs. bulk semiconducting properties that are required to form high-performance photoelectrodes.